CN112582682A - Lithium ion solid electrolyte with core-shell structure and preparation method thereof - Google Patents

Lithium ion solid electrolyte with core-shell structure and preparation method thereof Download PDF

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CN112582682A
CN112582682A CN202011448363.3A CN202011448363A CN112582682A CN 112582682 A CN112582682 A CN 112582682A CN 202011448363 A CN202011448363 A CN 202011448363A CN 112582682 A CN112582682 A CN 112582682A
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廖健淞
陈庆
司文彬
白涛
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Chengdu New Keli Chemical Science Co Ltd
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Abstract

The invention relates to the field of lithium batteries, and discloses a lithium ion solid electrolyte with a core-shell structure and a preparation method thereof. The preparation method comprises the following preparation processes: (1) mixing Li2CO3、Al2O3、TiO2And NH4H2PO4Mixing, calcining, cooling, grinding and sieving to obtain nuclear layer powder; (2) reacting LiOH & H2O、H3BO3、NH4H2PO4And NH4F, adding the mixture into deionized water, uniformly stirring, adjusting the pH value, adding silica sol, and mechanically stirring to obtain sol; (3) mixing the core layer powder with Al (H)2PO4)3Adding into sol for spray drying, sintering the obtained precursor material, cooling, grinding, washing and drying to obtain the lithium ion solid state material with the core-shell structureAn electrolyte. Compared with the common inorganic solid electrolyte, the core-shell structure inorganic solid electrolyte prepared by the invention has the advantages that the complete and compact electronic shielding layer is formed on the surface of the matrix material, the electrochemical window is wide, the ionic conductivity is high, and the application prospect is good.

Description

Lithium ion solid electrolyte with core-shell structure and preparation method thereof
Technical Field
The invention relates to the field of lithium batteries, and discloses a lithium ion solid electrolyte with a core-shell structure and a preparation method thereof.
Background
In recent years, rapid development in the field of new energy power generation puts new requirements on matched energy storage systems. In the updating and upgrading of energy storage batteries, lithium ion batteries have become an important research field due to various advantages of the lithium ion batteries, and have been practically applied to a large number of energy storage projects to achieve certain results. With the development of high and new technologies, lithium ion batteries have been widely used in various fields such as electric vehicles, smart phones, energy storage, and the like due to their advantages of high working voltage, high energy density, no memory effect, long cycle life, no pollution, and the like.
The lithium battery mainly comprises a positive electrode, a negative electrode and an electrolyte, wherein the electrolyte is used as a channel for Li + to be conducted on the positive electrode and the negative electrode, and plays an important role. The performance of the electrolyte directly affects the performance indexes of the lithium battery, such as capacity, use temperature, safety, cycle performance and the like. With the continuous improvement of the requirements of people on the safety, the energy density and the like of the lithium ion battery, the lithium ion battery with the traditional liquid electrolyte has the potential safety hazards of electrolyte leakage, volatilization, combustion, explosion and the like caused by the fact that short circuit is easy to occur even when the lithium ion battery is impacted. Therefore, the solid electrolyte is used as a high-safety electrolyte system, has the unique advantages of avoiding the internal short circuit of the battery, preventing the leakage of the electrolyte, not containing flammable and explosive components and the like, and shows wide application prospect.
Lithium ion inorganic solid electrolyte (also called lithium fast ion conductor) with high Li+Electrical conductivity and Li+The transference number and the activation energy of the electric conduction are low, the high temperature resistance is good, and the high-specific energy lithium ion battery has good application prospect in large-scale power lithium ion batteries. The lithium ion inorganic solid electrolyte is used for replacing an organic liquid electrolyte, so that the defects of internal short circuit and liquid leakage of the battery can be overcome, and the use safety of the lithium ion battery is improved. Therefore, the research on lithium ion solid electrolyte is always one of the hot problems in the research field of lithium ion battery materials.
Chinese patent application No. 201811293141.1 discloses a NASICON type lithium ion solidSolid electrolyte with the stoichiometric formula Li, its preparation method and its application1+xAlxTi2-x(PO4)3Wherein x is more than or equal to 0 and less than or equal to 0.5. The solid electrolyte with excellent performance is synthesized by controlling preparation process parameters such as temperature rise rate, pre-sintering temperature, pre-sintering time, calcining temperature, calcining time and the like, so that the room-temperature ionic conductivity of the solid electrolyte exceeds 10-4S/cm。
The Chinese patent application No. 201810073661.5 discloses a method for preparing a solid electrolyte membrane and a lithium battery, wherein the method for preparing the solid electrolyte membrane comprises the following steps: mixing polyoxyethylene and conductive lithium salt, adding the mixture into an acetonitrile solvent to form a mixed solution, and stirring the mixed solution at 15-25 ℃ for 4-16 hours until the conductive lithium salt is completely dissolved to form the electrolyte colloid. Adding an inorganic electrolyte into the electrolyte colloid, wherein the mass fraction of the inorganic electrolyte in the electrolyte colloid is 1-30%; the inorganic electrolyte comprises Li1+xAlxTi2–x(PO4)3(LATP), wherein x is more than or equal to 0.2 and less than or equal to 0.4. And (3) stirring for 6-24 hours at 15-25 ℃ until the inorganic electrolyte is completely dissolved to form the gel-state composite electrolyte. And (4) coating the gel-state composite electrolyte on a substrate, pressing the substrate to be flat, drying the substrate in vacuum at the temperature of 20-25 ℃, and removing the acetonitrile solvent to prepare the solid electrolyte membrane.
According to the above, in the existing schemes, research on inorganic solid electrolytes for lithium batteries mainly focuses on crystalline lithium ion solid electrolytes having LISICON (lithium zinc germanate) structure, NASICON (sodium super ionic CONductor) structure, perovskite-type structure and garnet-like structure, and oxide, sulfide, oxide and sulfide mixed glassy lithium ion solid electrolytes, however, the existing stepless solid electrolytes generally have the defects of narrow electrochemical window and unsatisfactory conductivity.
Disclosure of Invention
The inorganic solid electrolyte of the lithium ion battery which is widely applied at present generally has the defects of narrow electrochemical window and non-ideal ionic conductivity, and the development and application of the inorganic solid electrolyte in the lithium battery are influenced.
The invention solves the problems through the following technical scheme:
a preparation method of a lithium ion solid electrolyte with a core-shell structure comprises the following specific steps:
(1) firstly, Li2CO3、Al2O3、TiO2And NH4H2PO4Uniformly mixing, adding the mixture into an alumina crucible, calcining the mixture in a muffle furnace, naturally cooling the mixture to room temperature to obtain core material powder, and finally grinding the powder and sieving the powder to obtain core layer powder;
(2) firstly, LiOH. H2O、H3BO3、NH4H2PO4And NH4F is added into deionized water, stirred until the solution is fully dissolved, then ammonia water is used for adjusting the pH value, and Li is obtained after reaction0.15B0.95(PO4)0.9F0.3Adding silica sol into the precursor, and finally mechanically stirring to obtain sol;
(3) firstly, adding the nuclear layer powder obtained in the step (1) into the sol obtained in the step (2), and then adding Al (H)2PO4)3And after uniformly mixing, carrying out spray drying to obtain a precursor material with a core-shell structure, then placing the obtained precursor material with the core-shell structure in a muffle furnace for heating and sintering, naturally cooling to room temperature after the heating and sintering, and finally grinding, washing and drying to obtain the lithium ion solid electrolyte with the core-shell structure.
As is well known, the research on the lithium ion inorganic solid electrolyte is mainly focused on the crystalline lithium ion solid electrolyte having LISICON structure, NASICON structure, perovskite structure, garnet-like structure, and the oxide, sulfide, oxide and sulfide mixed glassy lithium ion solid electrolyte. The research not only solves the safety problem of the lithium battery electrolyte from the source, but also can work in a high-temperature environment, shows the advantages that other electrolyte systems do not have, and particularly hasLi with NASICON structure1+xAlxTi2-x(PO4)3The (LATP) is a lithium ion inorganic solid electrolyte capable of conducting lithium ions at a high rate, and is excellent in application performance. The invention mainly adopts NASICON structure inorganic electrolyte for research and application.
The invention uses Li2CO3、Al2O3、TiO2And NH4H2PO4Calcining in a muffle furnace as a raw material, and reacting to obtain Li with a NASICON structure by controlling the temperature and time of calcination1.1Al0.1Ti1.9(PO4)3。
Preferably, the calcining temperature in the step (1) is 700-900 ℃, and the time is 4-6 h; the core material powder is Li1.1Al0.1Ti1.9(PO4)3。
Li of NASICON structure1.1Al0.1Ti1.9(PO4)3Has high ion conductivity up to 10-4S/cm, however, Li due to the inclusion of a variable valence titanium ion1.1Al0.1Ti1.9(PO4)3When in contact with a negative electrode material of low potential, Ti4+Will be reduced to Ti3+The electron conductance is generated, resulting in a narrow electrochemical window. Although the existing ion doping technology can improve the room-temperature ion conductivity to a certain extent, the problem that the room-temperature ion conductivity is reduced at a low potential cannot be solved, so that Li1.1Al0.1Ti1.9(PO4)3When used as a solid electrolyte for a lithium ion battery, it is difficult to avoid short-circuiting of the battery due to the generation of electron conductance.
Preferably, the mesh number of the screen in the step (1) is 800-900 meshes.
In the preferred embodiment of the present invention, in the step (1), the raw materials are in a ratio of Li in terms of molar number2CO31.1 mol of Al2O30.1 mol, TiO23.8 mol, NH4H2PO46 mol of a compound;
the invention calcines the obtained product Li1.1Al0.1Ti1.9(PO4)3Grinding and sieving to obtain core material powder, and then obtaining core material Li1.1Al0.1Ti1.9(PO4)3The surface is coated with a layer of compact shell material, preferably Li in the invention0.15B0.95(PO4)0.9F0.3. The shell material can be in full surface contact with the core material, has a wide electrochemical window (the electrochemical window is more than 5V), and can form a complete and compact electronic shielding layer on the surface of the core material due to lower electronic conductivity, so that external electrons are shielded by the shell material and cannot be in contact with the core material, and the redox reaction of the core material is effectively avoided; meanwhile, the shell material has high ionic conductivity, does not influence the conduction of lithium ions, and effectively solves the problem of narrow electrochemical window of the inorganic solid electrolyte with the NASICON structure.
According to the principle, the specific operation method of the invention is to use LiOH & H2O、H3BO3、NH4H2PO4And NH4F is taken as a raw material, added into deionized water and stirred until the materials are fully dissolved, ammonia water is used for adjusting the pH value, and Li is obtained through reaction0.15B0.95(PO4)0.9F0.3A precursor; and silica sol is further added, preferably alkaline silica sol, the alkaline silica sol has a large surface area due to the fact that the diameter of colloidal particles of the alkaline silica sol is nano-scale (10-20 nm), the particles are colorless and transparent, the natural color of a covered object is not affected, meanwhile, the viscosity is low, the dispersibility and the permeability are good, when the moisture of the silica sol is evaporated, the colloidal particles can be firmly attached to the surface of an object, and the silica sol is a good adhesive and an additive. Therefore, the invention prepares Li0.15B0.95(PO4)0.9F0.3And adding alkaline silica sol into the precursor to obtain the sol shell material.
Preferably, the pH value is adjusted to 8-9 in the step (2).
Preferably, the silica sol in the step (2) is an alkaline silica sol with a solid content of silica of 35-45%.
Preferably, the rotation speed of the mechanical stirring in the step (2) is 250-450 r/min, and the time is 30-60 min.
Preferably, the sol in step (2) is a silica sol and Li0.15B0.95(PO4)0.9F0.3A mixture of precursors.
In the present invention, the raw materials in the step (2) are preferably LiOH. H in molar ratio2O0.15 mol, H3BO30.95 mol, NH4H2PO40.9 mol, NH40.3 mol of F, 15-20 mol of deionized water and 1-3 mol of silicon dioxide in the silica sol.
The invention adds nuclear layer powder into shell layer sol, then adds Al (H)2PO4)3Mixing homogeneously, Al (H)2PO4)3Is a good film-forming agent, and can be spray-dried to obtain Li0.15B0.95(PO4)0.9F0.3Precursor coated Li1.1Al0.1Ti1.9(PO4)3And finally, sintering the precursor material of the powder with the core-shell structure at high temperature to obtain the core-shell structure inorganic solid electrolyte with a complete and compact electronic shielding layer on the surface.
Preferably, the heating rate of the heating sintering in the step (3) is 2-4 ℃/min, the temperature is increased to 900-1100 ℃, and the heat preservation sintering is carried out for 12-24 hours.
In a preferred embodiment of the present invention, the raw materials of step (3) are 100 parts by weight of the core layer powder and Li0.15B0.95(PO4)0.9F0.310-40 parts of precursor and Al (H)2PO4)31 to 3 parts by weight.
The lithium ion solid electrolyte with the core-shell structure prepared by the method not only has a wider electrochemical window, but also has higher ionic conductivity and good application prospect. Through testing, the lithium ion of the prepared core-shell structureThe electrochemical window of the sub-solid-state electrolysis is 5.4-5.6V (vs. Li/Li)+) The ionic conductivity is 7.2 to 7.4 x 10-4 S/m。
The invention provides a lithium ion solid electrolyte with a core-shell structure and a preparation method thereof, wherein Li is used2CO3、Al2O3、TiO2And NH4H2PO4Uniformly mixing, adding the mixture into an alumina crucible, calcining the mixture in a muffle furnace, naturally cooling the mixture to room temperature to obtain core material powder, and grinding and sieving the powder to obtain core layer powder for later use; reacting LiOH & H2O、H3BO3、NH4H2PO4And NH4Adding the F into deionized water, stirring to fully dissolve the F, adjusting the pH value by using ammonia water, adding silica sol, and mechanically stirring to obtain sol; adding the core layer powder into the sol, and adding Al (H)2PO4)3And after uniform mixing, spray drying to obtain a precursor material with a core-shell structure, placing the obtained precursor material with the core-shell structure in a muffle furnace, heating and sintering, naturally cooling to room temperature after the sintering is finished, and grinding, washing and drying to obtain the material.
Compared with the prior art, the invention provides a lithium ion solid electrolyte with a core-shell structure and a preparation method thereof, and the lithium ion solid electrolyte has the outstanding characteristics and excellent effects that:
1. a method for preparing a lithium ion solid electrolyte with a core-shell structure by forming a compact electromagnetic shielding layer on the surface of an inorganic electrolyte with a NASICON structure is provided.
2. The cladding layer material is in full surface contact with the core layer matrix material, the cladding is firm, the cladding layer has a wide electrochemical window, and a complete and compact electronic shielding layer is formed on the surface of the core layer matrix material, so that external electrons are shielded by the outer layer material and cannot be in contact with the matrix material, the redox reaction of the matrix material is effectively avoided, and meanwhile, the cladding layer material also has high ionic conductivity and cannot influence the conduction of lithium ions.
3. The lithium ion solid electrolyte with the core-shell structure prepared by the invention has excellent service performance and excellent application prospect.
Drawings
FIG. 1 is a process flow diagram of the preparation of a lithium ion solid electrolyte with a core-shell structure by the method of the present invention; wherein: 1-adding core raw materials into a crucible; 2-sintering the first material in a muffle furnace; 3-core layer particles; 4-grinding and screening the core layer powder; 5, preparing sol; 6-nuclear layer powder, sol, Al (H)2PO4)3Mixing; 7-spray drying; 8-sintering in a muffle furnace II; 9-solid electrolyte powder.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1
(1) Firstly, Li2CO3、Al2O3、TiO2And NH4H2PO4Uniformly mixing, adding the mixture into an alumina crucible, calcining the mixture in a muffle furnace I, naturally cooling the mixture to room temperature to obtain core material powder, and finally grinding and sieving the powder to obtain core layer powder; the calcining temperature is 780 ℃ and the time is 5 h; the core material powder is Li1.1Al0.1Ti1.9(PO4)3(ii) a The mesh number of the sieve is 800 meshes;
the raw materials are in a molar ratio of Li2CO31.1 mol of Al2O30.1 mol, TiO23.8 mol, NH4H2PO46 mol of a compound;
(2) firstly, LiOH. H2O、H3BO3、NH4H2PO4And NH4F is added into deionized water, stirred until the solution is fully dissolved, then ammonia water is used for adjusting the pH value, and Li is obtained after reaction0.15B0.95(PO4)0.9F0.3Adding silica sol into the precursor, and finally mechanically stirring to obtain sol; adjusting the pH valueTo 8.5; the silica sol is alkaline silica sol with the solid content of 39 percent; the rotation speed of mechanical stirring is 360r/min, and the time is 50 min; the sol is silica sol and Li0.15B0.95(PO4)0.9F0.3A mixture of precursors;
the raw materials are in molar ratio of LiOH. H2O0.15 mol, H3BO30.95 mol, NH4H2PO40.9 mol, NH4F0.3 mol, deionized water 17 mol and silica sol 2 mol;
(3) firstly, adding the nuclear layer powder obtained in the step (1) into the sol obtained in the step (2), and then adding Al (H)2PO4)3Uniformly mixing, carrying out spray drying to obtain a precursor material with a core-shell structure, placing the obtained precursor material with the core-shell structure in a muffle furnace II, heating and sintering, naturally cooling to room temperature after the heating and sintering are finished, and finally grinding, washing and drying to obtain the lithium ion solid electrolyte with the core-shell structure; the heating rate of heating sintering is 3 ℃/min, the temperature is raised to 980 ℃, and the heat preservation sintering is carried out for 20 h;
the raw materials comprise 100 weight parts of nuclear layer powder and Li0.15B0.95(PO4)0.9F0.330 parts of precursor and Al (H)2PO4)32 parts by weight.
The preparation process is shown in the attached figure 1, wherein: 1-adding core raw materials into a crucible; 2-sintering the first material in a muffle furnace; 3-core layer particles; 4-grinding and screening the core layer powder; 5, preparing sol; 6-nuclear layer powder, sol, Al (H)2PO4)3Mixing; 7-spray drying; 8-sintering in a muffle furnace II; 9-solid electrolyte powder.
The ionic conductivity and electrochemical window of the lithium ion solid electrolyte with the core-shell structure prepared in example 1 are shown in table 1.
Example 2
(1) Firstly, Li2CO3、Al2O3、TiO2And NH4H2PO4Mixing, adding into alumina crucible, calcining in muffle furnace, and naturally cooling to roomHeating to obtain core material powder, and finally grinding and sieving the powder to obtain core layer powder; the calcining temperature is 750 ℃, and the calcining time is 5.5 h; the core material powder is Li1.1Al0.1Ti1.9(PO4)3(ii) a The number of the sieved meshes is 900 meshes;
the raw materials are in a molar ratio of Li2CO31.1 mol of Al2O30.1 mol, TiO23.8 mol, NH4H2PO46 mol of a compound;
(2) firstly, LiOH. H2O、H3BO3、NH4H2PO4And NH4F is added into deionized water, stirred until the solution is fully dissolved, then ammonia water is used for adjusting the pH value, and Li is obtained after reaction0.15B0.95(PO4)0.9F0.3Adding silica sol into the precursor, and finally mechanically stirring to obtain sol; adjusting the pH value to 8; the silica sol is alkaline silica sol with the solid content of 38 percent; the rotation speed of mechanical stirring is 300r/min, and the time is 50 min; the sol is silica sol and Li0.15B0.95(PO4)0.9F0.3A mixture of precursors;
the raw materials are in molar ratio of LiOH. H2O0.15 mol, H3BO30.95 mol, NH4H2PO40.9 mol, NH4F0.3 mol, deionized water 16 mol and silica sol 1.5 mol;
(3) firstly, adding the nuclear layer powder obtained in the step (1) into the sol obtained in the step (2), and then adding Al (H)2PO4)3Uniformly mixing, carrying out spray drying to obtain a precursor material with a core-shell structure, placing the obtained precursor material with the core-shell structure in a muffle furnace, heating and sintering, naturally cooling to room temperature after the sintering is finished, and finally grinding, washing and drying to obtain the lithium ion solid electrolyte with the core-shell structure; the heating rate of the heating sintering is 2 ℃/min, the temperature is raised to 950 ℃, and the heat preservation sintering is carried out for 22 hours;
the raw materials comprise 100 weight parts of nuclear layer powder and Li0.15B0.95(PO4)0.9F0.3Precursor 20 parts by weight, Al (H)2PO4)31.5 parts by weight.
The ionic conductivity and electrochemical window of the lithium ion solid electrolyte with the core-shell structure prepared in example 2 are shown in table 1.
Example 3
(1) Firstly, Li2CO3、Al2O3、TiO2And NH4H2PO4Uniformly mixing, adding the mixture into an alumina crucible, calcining the mixture in a muffle furnace, naturally cooling the mixture to room temperature to obtain core material powder, and finally grinding the powder and sieving the powder to obtain core layer powder; the calcining temperature is 850 ℃, and the time is 4.5 h; the core material powder is Li1.1Al0.1Ti1.9(PO4)3(ii) a The number of the sieved meshes is 900 meshes;
the raw materials are in a molar ratio of Li2CO31.1 mol of Al2O30.1 mol, TiO23.8 mol, NH4H2PO46 mol of a compound;
(2) firstly, LiOH. H2O、H3BO3、NH4H2PO4And NH4F is added into deionized water, stirred until the solution is fully dissolved, then ammonia water is used for adjusting the pH value, and Li is obtained after reaction0.15B0.95(PO4)0.9F0.3Adding silica sol into the precursor, and finally mechanically stirring to obtain sol; adjusting the pH value to 8; the silica sol is alkaline silica sol with the solid content of 42 percent; the rotation speed of mechanical stirring is 400r/min, and the time is 40 min; the sol is silica sol and Li0.15B0.95(PO4)0.9F0.3A mixture of precursors;
the raw materials are in molar ratio of LiOH. H2O0.15 mol, H3BO30.95 mol, NH4H2PO40.9 mol, NH4F0.3 mol, deionized water 19 mol and silica sol 2.5 mol;
(3) firstly, adding the nuclear layer powder obtained in the step (1) into the step(2) To the sol obtained, Al (H) is then added2PO4)3Uniformly mixing, carrying out spray drying to obtain a precursor material with a core-shell structure, placing the obtained precursor material with the core-shell structure in a muffle furnace, heating and sintering, naturally cooling to room temperature after the sintering is finished, and finally grinding, washing and drying to obtain the lithium ion solid electrolyte with the core-shell structure; the heating rate of the heating sintering is 4 ℃/min, the temperature is increased to 1050 ℃, and the heat preservation sintering is carried out for 16 h;
the raw materials comprise 100 weight parts of nuclear layer powder and Li0.15B0.95(PO4)0.9F0.330 parts of precursor and Al (H)2PO4)32.5 parts by weight.
The ionic conductivity and electrochemical window of the lithium ion solid electrolyte with the core-shell structure prepared in example 3 are shown in table 1.
Example 4
(1) Firstly, Li2CO3、Al2O3、TiO2And NH4H2PO4Uniformly mixing, adding the mixture into an alumina crucible, calcining the mixture in a muffle furnace, naturally cooling the mixture to room temperature to obtain core material powder, and finally grinding the powder and sieving the powder to obtain core layer powder; the calcining temperature is 700 ℃, and the time is 6 h; the core material powder is Li1.1Al0.1Ti1.9(PO4)3(ii) a The mesh number of the sieve is 800 meshes;
the raw materials are in a molar ratio of Li2CO31.1 mol of Al2O30.1 mol, TiO23.8 mol, NH4H2PO46 mol of a compound;
(2) firstly, LiOH. H2O、H3BO3、NH4H2PO4And NH4F is added into deionized water, stirred until the solution is fully dissolved, then ammonia water is used for adjusting the pH value, and Li is obtained after reaction0.15B0.95(PO4)0.9F0.3Adding silica sol into the precursor, and finally mechanically stirring to obtain sol; adjusting the pH value to 8; silicon solutionThe glue is alkaline silica sol with solid content of 35 percent; the rotation speed of mechanical stirring is 250r/min, and the time is 60 min; the sol is silica sol and Li0.15B0.95(PO4)0.9F0.3A mixture of precursors;
the raw materials are in molar ratio of LiOH. H2O0.15 mol, H3BO30.95 mol, NH4H2PO40.9 mol, NH4F0.3 mol, deionized water 15 mol and silica sol 1 mol;
(3) firstly, adding the nuclear layer powder obtained in the step (1) into the sol obtained in the step (2), and then adding Al (H)2PO4)3Uniformly mixing, carrying out spray drying to obtain a precursor material with a core-shell structure, placing the obtained precursor material with the core-shell structure in a muffle furnace, heating and sintering, naturally cooling to room temperature after the sintering is finished, and finally grinding, washing and drying to obtain the lithium ion solid electrolyte with the core-shell structure; the heating rate of the heating sintering is 2 ℃/min, the temperature is increased to 900 ℃, and the heat preservation sintering is carried out for 24 hours;
the raw materials comprise 100 weight parts of nuclear layer powder and Li0.15B0.95(PO4)0.9F0.310 parts of precursor and Al (H)2PO4)31 part by weight.
The ionic conductivity and electrochemical window of the lithium ion solid electrolyte with the core-shell structure prepared in example 4 are shown in table 1.
Example 5
(1) Firstly, Li2CO3、Al2O3、TiO2And NH4H2PO4Uniformly mixing, adding the mixture into an alumina crucible, calcining the mixture in a muffle furnace, naturally cooling the mixture to room temperature to obtain core material powder, and finally grinding the powder and sieving the powder to obtain core layer powder; the calcining temperature is 900 ℃ and the calcining time is 4 hours; the core material powder is Li1.1Al0.1Ti1.9(PO4)3(ii) a The number of the sieved meshes is 900 meshes;
the raw materials are in a molar ratio of Li2CO31.1 mol of Al2O30.1 mol, TiO23.8 mol, NH4H2PO46 mol of a compound;
(2) firstly, LiOH. H2O、H3BO3、NH4H2PO4And NH4F is added into deionized water, stirred until the solution is fully dissolved, then ammonia water is used for adjusting the pH value, and Li is obtained after reaction0.15B0.95(PO4)0.9F0.3Adding silica sol into the precursor, and finally mechanically stirring to obtain sol; adjusting the pH value to 9; the silica sol is alkaline silica sol with solid content of 45 percent; the rotation speed of mechanical stirring is 450r/min, and the time is 30 min; the sol is silica sol and Li0.15B0.95(PO4)0.9F0.3A mixture of precursors;
the raw materials are in molar ratio of LiOH. H2O0.15 mol, H3BO30.95 mol, NH4H2PO40.9 mol, NH4F0.3 mol, deionized water 20 mol and silica sol 3 mol;
(3) firstly, adding the nuclear layer powder obtained in the step (1) into the sol obtained in the step (2), and then adding Al (H)2PO4)3Uniformly mixing, carrying out spray drying to obtain a precursor material with a core-shell structure, placing the obtained precursor material with the core-shell structure in a muffle furnace, heating and sintering, naturally cooling to room temperature after the sintering is finished, and finally grinding, washing and drying to obtain the lithium ion solid electrolyte with the core-shell structure; the heating rate of the heating sintering is 4 ℃/min, the temperature is raised to 1100 ℃, and the heat preservation sintering is carried out for 12 h;
the raw materials comprise 100 weight parts of nuclear layer powder and Li0.15B0.95(PO4)0.9F0.340 parts of precursor and Al (H)2PO4)33 parts by weight.
The ionic conductivity and electrochemical window of the lithium ion solid electrolyte with the core-shell structure prepared in example 5 are shown in table 1.
Example 6
(1) Firstly, Li2CO3、Al2O3、TiO2And NH4H2PO4Uniformly mixing, adding the mixture into an alumina crucible, calcining the mixture in a muffle furnace, naturally cooling the mixture to room temperature to obtain core material powder, and finally grinding the powder and sieving the powder to obtain core layer powder; the calcining temperature is 800 ℃, and the time is 5 h; the core material powder is Li1.1Al0.1Ti1.9(PO4)3(ii) a The mesh number of the sieve is 800 meshes;
the raw materials are in a molar ratio of Li2CO31.1 mol of Al2O30.1 mol, TiO23.8 mol, NH4H2PO46 mol of a compound;
(2) firstly, LiOH. H2O、H3BO3、NH4H2PO4And NH4F is added into deionized water, stirred until the solution is fully dissolved, then ammonia water is used for adjusting the pH value, and Li is obtained after reaction0.15B0.95(PO4)0.9F0.3Adding silica sol into the precursor, and finally mechanically stirring to obtain sol; adjusting the pH value to 8.5; the silica sol is alkaline silica sol with the solid content of 40 percent; the rotation speed of mechanical stirring is 350r/min, and the time is 45 min; the sol is silica sol and Li0.15B0.95(PO4)0.9F0.3A mixture of precursors;
the raw materials are in molar ratio of LiOH. H2O0.15 mol, H3BO30.95 mol, NH4H2PO40.9 mol, NH4F0.3 mol, deionized water 18 mol and silica sol 2 mol;
(3) firstly, adding the nuclear layer powder obtained in the step (1) into the sol obtained in the step (2), and then adding Al (H)2PO4)3Uniformly mixing, carrying out spray drying to obtain a precursor material with a core-shell structure, placing the obtained precursor material with the core-shell structure in a muffle furnace, heating and sintering, naturally cooling to room temperature after the sintering is finished, and finally grinding, washing and drying to obtain the lithium ion solid electrolyte with the core-shell structure; lifting of wineThe temperature rise rate of the warm sintering is 3 ℃/min, the temperature is raised to 1000 ℃, and the heat preservation sintering is carried out for 18 h;
the raw materials comprise 100 weight parts of nuclear layer powder and Li0.15B0.95(PO4)0.9F0.325 parts by weight of precursor, Al (H)2PO4)32 parts by weight.
The ionic conductivity and electrochemical window of the lithium ion solid electrolyte with the core-shell structure prepared in example 6 are shown in table 1.
Comparative example 1
Comparative example 1 lithium ion solid electrolytes prepared by directly using the core layer powder obtained in example 6 as an electrolyte have ionic conductivities and electrochemical windows shown in table 1.
Comparative example 2
(1) Firstly, Li2CO3、Al2O3、TiO2And NH4H2PO4Uniformly mixing, adding the mixture into an alumina crucible, calcining the mixture in a muffle furnace, naturally cooling the mixture to room temperature to obtain core material powder, and finally grinding the powder and sieving the powder to obtain core layer powder; the calcining temperature is 800 ℃, and the time is 5 h; the core material powder is Li1.1Al0.1Ti1.9(PO4)3(ii) a The mesh number of the sieve is 800 meshes;
the raw materials are in a molar ratio of Li2CO31.1 mol of Al2O30.1 mol, TiO23.8 mol, NH4H2PO46 mol of a compound;
(2) firstly, LiOH. H2O、H3BO3、NH4H2PO4And NH4F is added into deionized water, stirred until the solution is fully dissolved, then ammonia water is used for adjusting the pH value, and Li is obtained after reaction0.15B0.95(PO4)0.9F0.3A precursor;
the raw materials are in molar ratio of LiOH. H2O0.15 mol, H3BO30.95 mol, NH4H2PO40.9 mol, NH4F0.3 mol and deionized water 18 mol;
(3) adding the core-layer powder obtained in the step (1) into the precursor liquid obtained in the step (2), uniformly mixing, then carrying out spray drying to obtain a precursor material with a core-shell structure, then placing the obtained precursor material with the core-shell structure in a muffle furnace, heating and sintering, naturally cooling to room temperature after the heating and sintering, and finally grinding, washing and drying to obtain the lithium ion solid electrolyte with the core-shell structure; the heating rate of the heating sintering is 3 ℃/min, the temperature is raised to 1000 ℃, and the heat preservation sintering is carried out for 18 h;
the raw materials comprise 100 weight parts of nuclear layer powder and Li0.15B0.95(PO4)0.9F0.325 parts by weight of precursor, Al (H)2PO4)32 parts by weight.
Comparative example 2 No silica sol and Al (H) were added2PO4)3Directly mixing the nuclear layer powder with Li0.15B0.95(PO4)0.9F0.3And mixing, spraying and drying the precursor, and sintering.
The ionic conductivity and the electrochemical window of the prepared lithium ion solid electrolyte with the core-shell structure are shown in table 1.
The performance index testing method comprises the following steps:
(1) ionic conductivity: taking the solid electrolytes prepared in examples 1-6 and comparative examples 1-2, and carrying out isostatic pressing to obtain a solid electrolyte sheet; respectively placing an electrolyte sheet between two stainless steel blocking electrodes, and performing alternating current impedance spectrum test on the solid electrolyte by using an Autolab T1864 electrochemical workstation at the temperature range of 298-373K, wherein the test balance time is 24h at each temperature, and the test frequency range is 0.01-105Hz, the alternating current amplitude is 10mV, Zview software is used for fitting impedance data according to a corresponding equivalent circuit, the body resistance is deduced, and the ion conductivity is calculated according to a formula; as shown in table 1.
(2) Electrochemical window: taking the solid electrolytes prepared in examples 1-6 and comparative examples 1-2, and carrying out isostatic pressing to obtain a solid electrolyte sheet; stainless steel is used as a working anode, and metal lithium is used as counter currentAnd the electrode and the reference electrode are used for respectively clamping the formed solid electrolyte sheets in the middle to assemble the battery, the battery is stood for more than 6 hours at 50 ℃, and the linear sweep voltammetry test is carried out through an electrochemical workstation. The test voltage range of the linear sweep voltammetry test is 2.5-6.0V (vs Li)+/Li)), the scan rate was 1 mV/s.
As can be seen from Table 1: the solid electrolyte prepared by the invention has a stable core-shell coating structure, forms a charge shielding layer, has an electrochemical window which is obviously higher than that of a comparative example 1 and a comparative example 2, and has relatively stable improvement on the ionic conductivity; comparative example 1 has low ionic conductivity due to no coating; comparative example 2 has poor coating effect due to no addition of film forming agent, and has inferior ionic conductivity and electrochemical window to those of examples.
Table 1:
Figure 639974DEST_PATH_IMAGE002

Claims (10)

1. a preparation method of a lithium ion solid electrolyte with a core-shell structure is characterized by comprising the following specific steps:
(1) firstly, Li2CO3、Al2O3、TiO2And NH4H2PO4Uniformly mixing, adding the mixture into an alumina crucible, calcining the mixture in a muffle furnace, naturally cooling the mixture to room temperature to obtain core material powder, and finally grinding the powder and sieving the powder to obtain core layer powder; the raw materials are in a molar ratio of Li2CO31.1 mol of Al2O30.1 mol, TiO23.8 mol, NH4H2PO46 mol of a compound;
(2) firstly, LiOH. H2O、H3BO3、NH4H2PO4And NH4F is added into deionized water, stirred until the solution is fully dissolved, then ammonia water is used for adjusting the pH value, and Li is obtained after reaction0.15B0.95(PO4)0.9F0.3Adding silica sol into the precursor, and finally mechanically stirring to obtain sol; the raw materials are in molar ratio of LiOH. H2O0.15 mol, H3BO30.95 mol, NH4H2PO40.9 mol, NH40.3 mol of F, 15-20 mol of deionized water and 1-3 mol of silicon dioxide in silica sol;
(3) firstly, adding the nuclear layer powder obtained in the step (1) into the sol obtained in the step (2), and then adding Al (H)2PO4)3Uniformly mixing, carrying out spray drying to obtain a precursor material with a core-shell structure, placing the obtained precursor material with the core-shell structure in a muffle furnace, heating and sintering, naturally cooling to room temperature after the sintering is finished, and finally grinding, washing and drying to obtain the lithium ion solid electrolyte with the core-shell structure; the raw materials comprise 100 weight parts of nuclear layer powder and Li0.15B0.95(PO4)0.9F0.310-40 parts of precursor and Al (H)2PO4)31 to 3 parts by weight.
2. The preparation method of the lithium ion solid electrolyte with the core-shell structure according to claim 1, wherein the preparation method comprises the following steps: the calcining temperature in the step (1) is 700-900 ℃, and the time is 4-6 h.
3. The preparation method of the lithium ion solid electrolyte with the core-shell structure according to claim 1, wherein the preparation method comprises the following steps: the core material powder in the step (1) is Li1.1Al0.1Ti1.9(PO4)3。
4. The preparation method of the lithium ion solid electrolyte with the core-shell structure according to claim 1, wherein the preparation method comprises the following steps: the mesh number of the screening in the step (1) is 800-900 meshes.
5. The preparation method of the lithium ion solid electrolyte with the core-shell structure according to claim 1, wherein the preparation method comprises the following steps: and (3) adjusting the pH value to 8-9 in the step (2).
6. The preparation method of the lithium ion solid electrolyte with the core-shell structure according to claim 1, wherein the preparation method comprises the following steps: and (3) the silica sol in the step (2) is alkaline silica sol with the solid content of silicon dioxide of 35-45%.
7. The preparation method of the lithium ion solid electrolyte with the core-shell structure according to claim 1, wherein the preparation method comprises the following steps: the rotating speed of the mechanical stirring in the step (2) is 250-450 r/min, and the time is 30-60 min.
8. The preparation method of the lithium ion solid electrolyte with the core-shell structure according to claim 1, wherein the preparation method comprises the following steps: the sol in the step (2) is silica sol and Li0.15B0.95(PO4)0.9F0.3A mixture of precursors.
9. The preparation method of the lithium ion solid electrolyte with the core-shell structure according to claim 1, wherein the preparation method comprises the following steps: and (3) heating the temperature-rising sintering at a heating rate of 2-4 ℃/min to 900-1100 ℃, and carrying out heat-preservation sintering for 12-24 h.
10. The lithium ion solid electrolyte with the core-shell structure prepared by the method of any one of claims 1 to 9.
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CN115799620A (en) * 2023-01-06 2023-03-14 江苏蓝固新能源科技有限公司 Preparation method of coated solid electrolyte
CN115863748A (en) * 2022-12-01 2023-03-28 重庆太蓝新能源有限公司 Preparation method of solid electrolyte material
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115595588A (en) * 2022-10-27 2023-01-13 江阴市珞珈绿碳科技有限公司（Cn） Titanate-based anode corrosion inhibitor for molten carbonate electrolytic system and preparation method thereof
CN115863748A (en) * 2022-12-01 2023-03-28 重庆太蓝新能源有限公司 Preparation method of solid electrolyte material
CN115799620A (en) * 2023-01-06 2023-03-14 江苏蓝固新能源科技有限公司 Preparation method of coated solid electrolyte
CN116396052A (en) * 2023-06-05 2023-07-07 蓝固(常州)新能源有限公司 Core-shell-glassy solid electrolyte and preparation method and application thereof
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